JPH04313747A - Antistaticized photographic material - Google Patents

Abstract

PURPOSE:To obtain a photographic material having satisfactory photographic performance and transparency and antistaticness by using an electron transfer type boron polymer having an N-B complex structure. CONSTITUTION:The photographic material is antistaticized by the N-B complex structure electron transfer type boron polymer, preferably, the reaction product of a semipolar organic borom polymer specified in structure with a tertiary amine. The boron polymer can be used for any part of the photographic material, such as a support, an undercoat layer, a backing layer, and a hydrophilic colloidal layer, and gelatin is advantageously used for these photographic materials, but other hydrophilic colloids can be used. Since this boron polymer is good in affinity to the hydrophilic colloids, it can be added to the hydrophilic colloidal layers without any especial contrivance.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic materials with excellent antistatic properties, and more particularly to antistatic photographic materials using plastic films.

0002

BACKGROUND OF THE INVENTION Plastic films generally have strong electrostatic properties, and this often imposes many restrictions on their use. For example, in photographic light-sensitive materials, a support made of a plastic film such as polyethylene terephthalate is generally used, but such light-sensitive materials are easily charged, especially under low humidity conditions such as in winter. Charging is more likely to occur in recent years, when high-sensitivity photographic emulsions are coated at high speeds, or when high-sensitivity photosensitive materials are exposed to light through automatic printers, and anti-static measures are particularly important in such cases. .

[0003] When a photosensitive material is charged, the discharge causes so-called static marks, or foreign matter such as dust is attached, which causes pinholes, resulting in a significant deterioration of quality. This greatly reduces work efficiency. For this reason, antistatic agents are generally used in photosensitive materials, and in recent years, antistatic agents have been used such as fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants containing polyethylene oxide groups, or polymers. Compounds, polymers having sulfonic acid or phosphoric acid groups in the molecule, etc. are used.

In particular, many antistatic methods have been used, such as adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers.
No. 9-91165 and No. 49-121523 disclose examples in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, many of the above-mentioned antistatic agents have an adverse effect on photographic performance, and no antistatic agent has been found that can sufficiently satisfy both antistatic properties and photographic performance. JP-A-56-143430 and JP-A No. 56-1434
Although each publication No. 31 proposes crystalline metal oxides that have little effect on photographic performance, it is necessary to use large amounts of such compounds in order to obtain sufficient antistatic ability. However, in this case, there was a drawback that transparency was impaired.

[0006] Accordingly, an object of the present invention is to provide a photographic material that satisfies photographic performance and transparency and has sufficient antistatic ability.

Another object of the present invention is to provide an antistatic agent that provides sufficient antistatic ability without impairing photographic performance or transparency.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of intensive research into the above-mentioned problem, the present inventors have found that the above-mentioned object of the present invention is to provide a photographic material which is antistatic by a charge-transfer type boron polymer having an N-B complex structure;
Alternatively, it has been found that this can be achieved by providing a photographic material in which the charge-transfer type boron polymer is contained in a support, a subbing layer or a hydrophilic colloid layer.

The present invention will be explained in more detail below.

[0010] The charge transfer type boron polymer having an N-B complex structure used in the present invention is a reaction product of a semipolar organoboron polymer having a structure represented by the following general formula [I] and a tertiary amine. Preferably, especially the following general formula [I
A reaction product of a semipolar organoboron polymer having a structure represented by [I] or [III] and a tertiary amine is preferred.

[0011]

[Formula 1, q is 0 or 1, and when q=1, A is -(
X) represents a-(Y)b-(Z)c- group. Here, X and Z each represent an oxygen-containing hydrocarbon group having 100 or less carbon atoms and having at least one terminal ether residue, and Y represents an elementary group. Further, a, b and c are each 0 or 1. p is 5-2000. ]

00
12]

[In the formula, q is 0 or 1, and when q = 1, B is -(
X) represents a l-(Y)m-(Z)n- group. Here, X
and Z each represent an oxygen-containing hydrocarbon group having one terminal ether residue and a total number of carbon atoms of 200 or less, and Y represents a hydrocarbon group. Also, l, m and n are
Each is independently 0 or 1. R1 and R2 are each a hydrogen atom or a substituent having 15 or less carbon atoms,
Preferably it is a hydrogen atom. m and n are each 1 to 3
is an integer of 2 or more when m and n are each 2 or more
1 and R2 may be the same or different. ]

00
[13] The tertiary amine that reacts with the semipolar organoboron polymer is preferably one having 5 to 82 carbon atoms, particularly one having 5 to 30 carbon atoms. Moreover, those having at least one hydroxyl group are preferably used.

The charge transfer type boron polymer used as an antistatic agent in the present invention is a reaction product of at least one semipolar organic boron polymer represented by the general formula [I] and at least one tertiary amine. (However, the reaction product has a ratio of one boron atom to one basic nitrogen atom).

The semipolar organoboron polymer represented by the general formula [I] may be, for example, the following (a) or (b).
It can be manufactured by the following method.

(a) Method: One or more compounds represented by the following general formula [IV] are added to a total of 1 mol of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms. Triesterification reaction is carried out by reacting 1 mol of or 0.5 mol of boric anhydride.

[0017]

[In the formula, q is 0 or 1, and when q = 1, A is -(
X) represents a-(Y)b-(Z)c- group. (However, X and Z each represent an oxygen-containing hydrocarbon group having 100 or less carbon atoms and having one terminal ether residue, and Y represents a hydrocarbon group having 1 to 20 atoms, preferably 5 to 15 atoms.) It is. a, b and c are each 0 or 1. ]

Method (b): one or more diols containing di(glycerol)-borate or a di(glycerol)-borate residue in the middle having 206 or less carbon atoms, preferably 10 to 100, to polyether 3 to 84 carbon atoms, preferably 8 carbon atoms, per 1 mole of one or more of them.
~84 dicarboxylic acid (hereinafter referred to as a predetermined dicarboxylic acid), an ester of a lower alcohol having 4 or less carbon atoms and a predetermined dicarboxylic acid, or a halide of a predetermined dicarboxylic acid, or a halide having 4 to 15 carbon atoms, preferably A total of 1 mole of one or more of 8 to 15 diisocyanates (hereinafter referred to as predetermined diisocyanates) is reacted.

One or more semipolar organoboron polymers thus produced (hereinafter referred to as predetermined semipolar organoboron polymers) and a carbon atom having from 5 to 82 carbon atoms and having at least one hydroxyl group. , preferably 5 to 30 tertiary amines (hereinafter referred to as predetermined tertiary amines), and one or more boric acid atoms to one basic nitrogen atom. At the rate of
Pour into a closed or open reactor, under normal pressure, for 20~
If the reaction is carried out at 200°C, preferably 50 to 150°C, the antistatic agent of the present invention (hereinafter referred to as a predetermined charge-transfer type boron polymer) will be produced. At that time, if polar solvents such as alcohols, ethers, and ketones are coexisting,
Reactions can be carried out more easily.

The raw materials for producing the charge transfer type boron polymer of the present invention and the semipolar organic boron polymer which is its intermediate are as follows.

First, examples of the compound represented by the general formula [IV] which is a raw material in method (a) for producing a predetermined semipolar organic boron polymer include diglycerin, di(glycerin)-malonate, di(glycerin)-malonate, and di(glycerin)-malonate. ) - Maleato, Ji (
di(glycerin)-adipate, di(glycerin)-terephthalate, di(glycerin)-dodecanate, poly(9
mol)oxyethylene-di(glycerin ether), di(glycerin)-tolylene dicarbamate, di(glycerin)-methylenebis(4-phenylcarbamate), etc.; Examples of dicarboxylic acids include malonic acid, maleic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, dodecane dioic acid, dimer acid derived from linoleic acid, dodecylmaleic acid, dodecenyl Examples include maleic acid, octadecylmaleic acid, octadecenylmaleic acid, maleic acid linking polybutenyl groups with an average degree of polymerization of 20, and examples of the predetermined diisocyanate include ethylene diisocyanate, Hexamethylene diisocyanate, tolylene diisocyanate and methylene bis(4-phenylisocyanate)
etc.

Next, examples of the predetermined tertiary amine to be reacted with the predetermined semipolar organoboron polymer include diethyl-hydroxymethylamine, dimethyl-2-hydroxypropylamine, and methyl-di(2-hydroxyethyl-amine). , tri(2-hydroxyethyl)amine, hydroxymethyl-di(2-hydroxyethyl)amine, dibenzyl-2-hydroxypropylamine, cyclohexyl-di(2-hydroxyethyl)amine, di(hexadecyl)amine in ethylene oxide (1 ~25 mol) adduct, and propylene oxide (~25 mol) adduct of monobutylamine (
1 to 26 mol) adducts, etc.

In connection with the present invention, when the amine raw material to be reacted with the predetermined semipolar organoboron polymer is of a type other than the predetermined tertiary amine, that is, a primary or secondary amine, charge transfer type boron is used. Since the polymer is not successfully produced and the resulting product is an unstable compound, it is difficult to develop and maintain electrical conductivity.

Preferred specific examples of the charge transfer type boron polymer having an N-B complex structure (hereinafter referred to as the boron polymer of the present invention) used in the present invention are shown below.

[0025]

[C4]

[0026]

[C5]

[0027]

[C6]

[0028]

[C7]

[0029]

[Chemical formula 8]

[0030]

[Chemical formula 9]

[0031]

[Chemical formula 10]

Regarding the boron polymer of the present invention, for example, "Plastic Age" 1987, February issue, March issue,
It is described in detail in May issue, Japanese Patent Application Laid-Open No. 1-266153, etc., and these can also be used.

The boron polymer of the present invention can be applied anywhere in the photographic material. That is, it can be contained in the support, undercoat layer, back layer, and hydrophilic colloid layer.

As the hydrophilic colloid that can be used in the photographic material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, dextran, starch derivatives, etc. Sugar derivatives; various synthetic highly hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used.
Furthermore, gelatin hydrolysates and enzymatically decomposed products can also be used.

The hydrophilic colloid layer of the photographic material of the present invention is a layer using a hydrophilic colloid coated on a support, such as a photosensitive layer such as a silver halide emulsion layer, a backing layer, and a protective layer. , a non-photosensitive layer such as an intermediate layer, etc., but the boron polymer of the present invention may be used in any layer.

Furthermore, a surface protective layer, a back layer or an intermediate layer is provided.
If it consists of more than one layer, any of the layers may be used, and
It can also be used as an overcoat on the surface protective layer.

Since the boron polymer of the present invention has good affinity with hydrophilic colloids, it can be added to hydrophilic colloid layers without any special measures, and can be added in the same manner as other photographic additives. It can be added by any method. for example,
The boron polymer can be contained in the hydrophilic colloid layer by dispersing the boron polymer in water and adding it to the hydrophilic colloid coating solution, or by dispersing the boron polymer in the hydrophilic colloid solution and adding it. A surfactant may be used during dispersion.

Generally known curing agents can be used in the hydrophilic colloid layer, such as aldehydes, active vinyl compounds, active halogen compounds, mucohalogen acids, etc., preferably vinyl sulfone compounds, active halogen compounds, etc. A compound is used.

In the present invention, the amount of the boron polymer of the present invention used in the hydrophilic colloid layer can be arbitrarily selected depending on the purpose, and is not particularly limited.
Usually 0.5 to 20% based on the dry weight of hydrophilic colloid
0% by weight, preferably 1 to 100% by weight.

[0042] In order to apply the undercoat layer or back layer containing the boron polymer of the present invention, it is preferable to dissolve or disperse the polymer in a binder.

As the binder, any polymer commonly used in coatings can be used, such as gelatin, modified gelatin, polyvinyl alcohol, vinyl alcohol copolymer, carboxymethyl cellulose, polyacrylic acid, and acrylic acid copolymer. water-soluble polymers such as polyvinylpyrrolidone, vinylpyrrolidone copolymer, hydroxyethyl acrylate copolymer, cellulose derivatives such as diacetylcellulose, triacetylcellulose, nitrocellulose, acetylbutylcellulose, acetylpropylcellulose, phthaloxyacetylcellulose , styrene, α-methylstyrene, hydroxystyrene, vinyl acetate, alkyl (alkyl group having 1 to 4 carbon atoms) acrylate, alkyl (alkyl group having 1 to 4 carbon atoms) methacrylate,
Homopolymers such as vinyl chloride and vinylidene chloride, copolymerized polymers containing these monomers, copolymerized polymers containing maleic anhydride, soluble nylon, soluble polyester, acetals such as polyvinyl formal, polyvinyl acetal, and polyvinyl benzal, polyurethane, etc. I can do it.

Water or a common organic solvent can be used as a solvent for these dispersions or solutions. Examples of organic solvents include alcohols such as methanol, ethanol, and propanol; esters such as methyl acetate and ethyl acetate;
Chlorinated hydrocarbons such as methylene dichloride, ethylene dichloride, ethane tetrachloride, chlorocene, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and other methyl cellosolve, ethyl cellosolve, dioxane, methyl cellosolve acetate,
Examples include benzene, phenol, resorcinol, and cresol. These solvents can be used alone or in combination.

When a hydrophobic polymer is used as a binder without using an organic solvent, it is preferably used in the form of a water-dispersed copolymer.

The water-dispersed copolymer used in the undercoat layer or back layer can be synthesized by a known emulsion polymerization method. Further, when emulsion copolymerizing these monomers, it is advantageous to use a surfactant for emulsion polymerization. For example, protection of polyvinyl alcohol, partially saponified vinyl acetate, polyethylene oxide, polyethylene oxide derivatives, hydroxyethyl cellulose, methyl cellulose, styrene-maleic acid copolymer, vinyl acetate-maleic acid copolymer, methyl vinyl ether-maleic acid copolymer, etc. Colloids, cationic surfactants such as dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, dodecylisoquinolinium bromide, anionic surfactants such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylbenzenecarboxylate are advantageously used, and a nonionic surfactant may also be added if necessary.

As a polymerization initiator, organic or inorganic peroxides or persalts, such as acetyl peroxide, benzoyl peroxide, benzoylacetyl peroxide, lauryl peroxide, hydrogen peroxide, percarbonates, persulfates, Perborate can be used. In addition, inorganic oxygen-containing oxidizing sulfur compounds such as sulfur dioxide, sodium bisulfite, sodium sulfite, sodium metasulfite, ammonium sulfite, and water-soluble aliphatic tertiary amines such as triethanolamine and diethanolamine can also be used. .

The above copolymer is dispersed as fine particles in an aqueous dispersion medium and used as an aqueous copolymer composition for a subbing liquid or a back layer coating liquid. Depending on the purpose, water may be
% may be replaced by an organic solvent miscible with water (eg methanol or acetone). The copolymer obtained by the emulsion polymerization method is obtained as an aqueous dispersion of a fine-particle emulsion polymer, so-called latex.

The subbing liquid or back layer coating liquid containing the copolymer latex as a main component thus obtained contains 0.1 to 40% by weight of the above-mentioned copolymer component, and optionally contains surface active agents. The composition may contain additives such as a hydrophilic organic colloid, a matting agent, a lubricant, and a crosslinking agent.

Examples of crosslinking agents include so-called hardening agents for photographic gelatin, such as formaldehyde, aldehyde compounds such as glyoxal, mucochloric acid, tetramethylene-1,4-bis(ethyleneurea), hexamethylene-
Compounds with ethyleneimine groups such as 1,6-bis(ethyleneurea), methanesulfonic acid esters such as trimethylene-1,3-bismethanesulfonic acid ester, active vinyl compounds such as bisacryloylurea, metaxylene vinyl sulfonic acid, etc. , compounds having active halogens such as 2-methoxy-4,6-dichlorotriazine and 2-sodiumoxy-4,6-dichlorotriazine, compounds having epoxy groups such as bisphenol glycidyl ether, isocyanate carboxyl group-activated compounds, and Epoxy compounds etc. can be used. Of these,
Particularly preferred are compounds having ethyleneimine groups, methanesulfonic acid esters, epoxy compounds and compounds having active halogens.

[0051] In the present invention, the undercoat layer and back layer may contain a surfactant if necessary.

[0052] Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc., and preferably anionic surfactants and/or nonionic surfactants. It is a drug. As anionic surfactants and nonionic surfactants,
A variety of compounds, each known in the art, can be used.

Specific examples of surfactants preferably used in the undercoat layer and back layer in the present invention are shown below.

[0054]

[Chemical formula 11]

[0055]

[Chemical formula 12]

[0056]

[Chemical formula 13]

[0057]

[Chemical formula 14]

[0058]

[Chemical formula 15]

[0059]

[Chemical formula 16]

[0060]

[Chemical formula 17]

The amount of surfactant in the undercoat coating solution is preferably 0.05 to 20 g, particularly preferably 0.05 to 10 g, per liter of the undercoat coating solution.

[0062] The organic solvent-based coating liquid for the subbing liquid and backing layer is applied onto the plastic film by a known method. For example, it can be applied onto a plastic film by curtain coating, reverse roll coating, fountain air doctor coating, slide hopper coating, extrusion coating, dip coating, etc. The coating amount of the copolymer is preferably 0.01 to 20 g/m2, particularly preferably 0.03 to 15 g/m2. Drying of the subbing liquid and back layer coating liquid after coating can be performed by a known method. For example, hot air drying, infrared heating drying, heater roll drying, microwave drying, etc. can be used. The drying conditions at this time are preferably 60 to 150°C for several seconds to 10 minutes.

Before coating or after drying these subbing liquids and the upper layer coating liquid and back layer coating liquid provided as necessary, flame radiation treatment, plasma treatment, corona discharge treatment, Known surface treatments such as glow discharge treatment and ultraviolet irradiation treatment can be performed.

In the back layer of the present invention, as an antistatic agent, in addition to the boron polymer of the present invention, for example,
56059, crosslinked polymers having a vinylbenzyl quaternary ammonium salt in the polymer position, especially Alumina sol having an electrolyte as disclosed in Japanese Patent Publication No. 57-12979 or crystalline metal oxide fine particles as disclosed in Japanese Patent Application Laid-open No. 56-143431 may be used in combination.

[0065] If necessary, the back layer may be
A layer made of a higher fatty acid or a derivative thereof as disclosed in No. 238361 may be provided as the outermost layer,
The higher fatty acids or derivatives thereof include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as methylene chloride and carbon tetrachloride, ethers such as diethyl ether and dioxane, benzene, toluene, etc. or as a dispersion of water or water and a water-miscible organic solvent. The water-miscible organic solvent is a solvent represented by alcohols such as methanol and ethanol, ketones such as acetone, etc., and is a solvent that can be mixed with water in any proportion.

When the boron polymer of the present invention is applied to a subbing layer, a plastic film, preferably a polyester film or a cellulose ester film, is used as the support.

The polyester film used in the present invention includes a linear saturated polyester synthesized from an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative.

Specific examples of such polyesters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, and ethylene glycol, diethylene glycol, polyethylene glycol,
, 3-propanediol, 1,4-butanediol, 1
, 4-cyclohexanedimethanol and other condensates with glycols, such as polyethylene terephthalate, polyethylene 2,6 dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, etc., or copolymers thereof, and other resins. Also includes those obtained by blending small amounts of. Further examples include plastic film supports kneaded with white pigments such as titanium oxide and barium sulfate.

As the cellulose ester, cellulose acetate is preferred, particularly cellulose acetate having an oxidation degree of 56 to 62%. The amount of cellulose ester in the dope is preferably 3 to 50% by weight, particularly 15 to 25% by weight.

A plasticizer may be added to the cellulose ester for the purpose of improving the flexibility or moisture resistance of the film. As the plasticizer, triphenyl phosphate, biphenyl diphenyl phosphate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, etc. are used. The amount added can range from 2 to 20% by weight based on the cellulose ester, but the minimum amount that does not impair the flexibility of the membrane is desirable. In other words, 2~
About 15% by weight is good.

Furthermore, various dyes, ultraviolet absorbers, and infrared absorbers may be added singly or in combination for purposes such as optical filters. The amount added varies depending on the purpose of use and is not particularly limited.

[0072] Examples of the solvent for cellulose ester include methylene chloride, chloroform, tetrachloroethylene, dimethylacetamide and the like.

The cellulose ester film is prepared by heating the cellulose ester dope having the composition as described above, filtering it, casting it on a polished metal band or drum using a Hopper-Giesser, and partially drying it (for example, at 30 to 130°C for 1 hour). ~
After 15 minutes), it is stripped from the band or drum and further dried (for example, at 80 to 130°C for 5 to 40 minutes) to evaporate the remaining solvent.

[0074] There are no particular restrictions on the method for producing the cellulose ester film, and methods commonly used in the art can be preferably used. For the production of cellulose ester films, see, for example, U.S. Pat. No. 2,492,9
No. 78, No. 2,739,070, No. 2,739,
No. 069, No. 2,492,977, No. 2,336
, No. 310, No. 2,367,603, No. 2,49
British Patent No. 2,978, British Patent No. 2,607,704, British Patent No. 640,731, British Patent No. 735,892, Japanese Patent Publication No. 1973
-9074 publication, 49-4554 publication, 49-
The descriptions in Publication No. 5614 and the like can be referred to.

When applying the subbing liquid onto a polyester film, it is preferable to subject the surface of the polyester film to various surface activation treatments to make it hydrophilic before application. As a surface activation treatment, for example, U.S. Pat. No. 2,943,937
oxidizing agent solution treatment as described in the specification of US Patent No. 3,475,193, etc., ultraviolet absorption treatment as described in US Pat. Electric discharge treatment of corona discharge, UK patent No. 1,
Active gas irradiation treatment as described in US Pat. No. 215,234, flame treatment as described in US Pat. No. 3,590,107, and British Patent No. 997,09.
Examples include glow discharge treatment as described in No. 3 and the like.

In the present invention, a subbed plastic film, particularly a polyester film, is coated with a subbing resin composition containing a boron polymer of the present invention on at least one surface of the plastic film support before completion of orientation crystallization. After applying a liquid and drying, it is stretched in at least one direction and heat-set to complete oriented crystallization, or
Alternatively, it can be obtained by coating and drying the coating solution containing the boron polymer of the present invention on the plastic film support after completion of oriented crystallization.

When the boron polymer of the present invention is applied to a support, a biaxially oriented polyester film is preferably used as the support.

The polyester resin used in the biaxially stretched polyester film includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, ethylene glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, Polymers of condensates with glycols such as 1,4-butanediol and 1,4-cyclohexanedimethanol,
For example, polyethylene terephthalate, polyethylene 2,
Examples include 6 dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof.

[0079] As the polyester resin to be biaxially stretched,
Polyethylene terephthalate (hereinafter abbreviated as PET) is preferred. Biaxially stretched PET resin film does not penetrate water, has excellent smoothness, excellent mechanical properties such as tensile strength and tear strength, excellent dimensional stability such as heat shrinkage, and chemical resistance during development processing. It is excellent in

The intrinsic viscosity of the polyester resin to be biaxially stretched, measured at 20°C in a mixed solvent of phenol/tetrachloroethane (60/40 weight ratio), is preferably 0.40 or more, more preferably 0.5 to 0. It is .8.

[0081] The biaxially stretched polyester film contains pigments,
It may contain additives such as colorants such as dyes, optical brighteners, antistatic agents, antioxidants, ultraviolet absorbers, and polymers other than polyester.

When the boron polymer of the present invention is applied to a support, it can be added at any stage up to film formation. That is, it may be added during the polymerization reaction of the polyester resin, it may be kneaded with the polyester resin at a temperature higher than the melting point of the resin, it may be added when melt-molding the film, but it may be added during the melt-molding of the film. It is preferable to do so.

The amount of the boron polymer of the present invention added to the support film is 0.05 to 20% by weight, preferably 0.5 to 10% by weight, based on the film resin.

The kneading machine for kneading and dispersing the boron polymer of the present invention into polyester includes an extruder having a rotor or blades for kneading, a twin-screw kneading extruder that rotates in the same or different directions, and a single-screw conti. Continuous kneading machines such as a Nyusu kneader, batch kneading machines such as a three-roll mixer, a Banbury mixer, a Henschel mixer, and a kneader are used.

The polyester composition obtained by the above-mentioned kneading may be once pelletized and then subjected to film forming, or may be subjected to film forming while in a molten state. In either method, the composition may be molded as it is, or a high-concentration composition, a so-called masterbatch, may be prepared, diluted, and molded.

To form a film, the polyester composition obtained by kneading is extruded in a molten state through a slit die, ground on a rapidly cooling surface such as a rotating drum to form an amorphous sheet, and then heated to a temperature higher than the glass transition temperature of the polyester. The film can be stretched sequentially in one axis in the longitudinal or transverse direction or simultaneously in two axes. At this time, in order to satisfy the mechanical strength and dimensional stability of the film support, an area ratio of 4 to 16
It is preferred that the stretching be carried out by a factor of 6 to 12 times, more preferably by a factor of 6 to 12 times. After stretching, it is preferable to carry out heat setting and heat relaxation.

The thickness of the film support obtained above is:
30-300 μm is preferable, more preferably 50-2
It is 50 μm. If it is thinner than 30 μm, it will not be stiff as a support and will wrinkle easily. Moreover, if the thickness exceeds 250 μm, there will be disadvantages such as being too thick and making handling inconvenient.

[0088] As the above-mentioned support, a polyester film laminated with a layer containing the boron polymer of the present invention on at least one side can also be used.

Various methods can be applied to laminate the boron polymer-containing layers. In other words, a co-extrusion method involves extruding a boron polymer-containing polyester in a molten state and a regular polyester in a molten state from respective dies or a common die and laminating them in the molten state. There are extrusion lamination methods, in which polyester is melt-extruded into films and laminated, and dry lamination methods, in which preformed polyester films are bonded together using an adhesive.

The photographic materials according to the present invention include ordinary black-and-white silver halide photographic materials (for example, black-and-white photographic materials, black-and-white photographic materials for X-ray, black-and-white photographic materials for printing, etc.), and ordinary multilayer photographic materials. Examples include color photosensitive materials (for example, color negative films, color reversal films, color positive films, color negative films for movies, etc.), infrared light sensitive materials for laser scanners, and the like.

[0091]

[Examples] The present invention will be explained in detail with reference to Examples below.

Example 1 One side (surface) of triacetyl cellulose film support
was subjected to subbing processing, and then, with the support in between, layers having the following composition were successively created from the support side on the opposite side (back side) to the surface on which the subbing processing was applied.

Back side first layer Alumina sol AS-100 (aluminum oxide) 0.8 g
(Manufactured by Nissan Chemical Industries, Ltd.) Second layer on the back: Diacetylcellulose

100 mg stearic acid

10 mg Silica fine particles (average particle size 0.2 μm)
Further, each layer having the composition shown in Photosensitive Material Prescription 1 below was successively formed on the undercoated surface of a triacetyl cellulose film support from the support side to prepare photosensitive material sample 101.

Photosensitive material formulation 1 First layer; antihalation layer (HC) black colloidal silver

0.15 g UV absorber (UV-1)

0.20 g Compound (CC-1)

0.02 g High boiling point solvent (Oi
l-1)
0.20 g High boiling point solvent (Oil-2)
0.20 g
gelatin

1.6 g second layer; intermediate layer (IL-1) gelatin

1.3 g Third layer; low sensitivity red-sensitive emulsion layer (R
-L) Silver iodobromide emulsion (average grain size 0.3 μm)
0.
4 g (average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4
μm)
0.3 g (
Average iodine content: 8.0 mol%) Sensitizing dye (S-1
) 3.2×
10-4 (mol/silver 1 mol) Sensitizing dye (S-2)
3.2×10
-4 (mol/silver 1 mol) Sensitizing dye (S-3)
0.2×10-4
(mol/silver 1 mol) Cyan coupler (C-1)

0.50 g Cyan coupler (C-2)

0.13 g Colored cyan coupler (CC-1)
0.07 g DIR compound (D-1)

0.006g DIR compound (D-2
)
0.01 g High boiling point solvent (O
il-1)
0.55 g gelatin
1
．． 0 g 4th layer; high sensitivity red-sensitive emulsion layer (R-H)
Silver iodobromide emulsion (average grain size 0.7 μm)
0.9 g
(Average iodine content 7.5
Mol%) Sensitizing dye (S-1)
1.7×10-4 (mol/silver 1 mol) Sensitizing dye (S-2)
1.6×10-4 (mol/1 mole of silver)
Sensitizing dye (S-3)
0.1 x 10-4 (mol/1 mol of silver)
Cyan coupler (C-2)
0.23g
Colored cyan coupler (CC-1)
0.03 gD
IR compound (D-2)
0.02g
High boiling point solvent (Oil-1)
0.
25 g gelatin

1.0 g 5th layer; intermediate layer (IL-
2) Gelatin

0.8 g 6th layer; low-sensitivity green-sensitive emulsion layer (G
-L) Silver iodobromide emulsion (average grain size 0.4 μm)
0.
6 g (average iodine content 8.0 mol%) Silver iodobromide emulsion (average grain size 0.3
μm)
0.2 g (
Average iodine content: 2.0 mol%) Sensitizing dye (S-4
) 6.7×
10-4 (mol/silver 1 mol) Sensitizing dye (S-5)
0.8×10
-4 (mol/mol of silver) Magenta coupler (M-1
)
0.17 g magenta coupler (M-
2)
0.43 g Colored magenta coupler (CM-1)
0.10 g DIR compound (D-3)

0.02 g High boiling point solvent (Oil-2
)
0.7 g gelatin

1.0
g7th layer; Highly sensitive green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm)
0.9g
(Average iodine content 7.5 mol%)
Sensitizing dye (S-6)
1.1×10-4 (mol/1 mol of silver)
Sensitizing dye (S-7)
2.0×10-4 (mol/silver 1 mol) Sensitizing dye (S-8)
0.3 x 10-4 (mol/silver 1 mol) Magenta coupler (M-1)
0.30 g Magenta coupler (M-2)
0.13 g Colored magenta coupler (CM-1)
0.04 g DIR compound (D-3)
0.004g High boiling point solvent (Oil-2)
0.35g
gelatin

1.0 g 8th layer; yellow filter layer (Y
C) Yellow colloidal silver

0.1 g Compound (HS-1)

0.07 g Compound (HS-2)

0.07 g compound (
SC-1)
0.12g
High boiling point solvent (Oil-2)
0.1
5 g gelatin

1.0 g 9th layer; low sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.3 μm)

0.25 g (Average iodine content 2.0 mol%) Silver iodobromide emulsion (average grain size 0.4 μm)
0.25g
(Average iodine content 8.0 mol%) Sensitizing dye (
S-9) 5
．． 8×10-4 (mol/silver 1 mol) Yellow coupler (Y-1)
0.6 g Yellow coupler (Y-2)
0.32 g DIR compound (D-1)
0.003g DI
R compound (D-2)
0.006g
High boiling point solvent (Oil-2)
0.1
8 g gelatin

1.3 g 10th layer; Highly sensitive blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 μm
)
0.5 g (average iodine content 8.5 mol%) Sensitizing dye (S-10)
3×10
-4 (mol/silver 1 mol) Sensitizing dye (S-11)
1.2×10-4
(Mole/1 mole of silver) Yellow coupler (Y-1)

0.18 g Yellow coupler (Y-2)

0.10 g High boiling point solvent (Oil-2)

0.05 g gelatin

1.0 g
11th layer; 1st protective layer (PRO-1) Silver iodobromide (average grain size 0.08 μm)
0.3
g Ultraviolet absorber (UV-1)
0
．． 07 g Ultraviolet absorber (UV-2)

0.10 g Compound (HS-1)

0.2 g Compound (HS-2)

0.1 g high boiling point solvent (
Oil-1)
0.07 g High boiling point solvent (Oil-3)
0.07g
gelatin

0.8 g 12th layer; 2nd protective layer (PRO-
2) Compound A

0.04 g Compound B

0.004g polymethyl methacrylate (average particle size 3μm)
0.02 g Methyl methacrylate: Ethyl methacrylate: 0.
13 g Copolymer of methacrylic acid = 3:3:4 (weight ratio) (average particle size 3 μm) Gelatin

0.5 g The silver iodobromide emulsion used in the 10th layer was prepared in the following manner.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol %) having an average grain size of 0.33 μm as seed crystals.

Solution <G-1> was heated to a temperature of 70°C and a pAg of 7.
8. While maintaining the pH at 7.0 and stirring well, a seed emulsion equivalent to 0.34 mol was added.

(Formation of internal high iodine phase - core phase) After that, while maintaining the flow rate ratio of solution <H-1> and solution <S-1> at 1:1, the flow rate was accelerated (at the end of The addition took 86 minutes at a flow rate of 3.6 times the initial flow rate.

(Formation of external low iodide phase - shell phase) Next, while maintaining pAg 10.1 and pH 6.0, the solution <
H-2> and solution <S-2> were added at an accelerated flow rate of 1:1 (final flow rate 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.

The obtained emulsion had an average grain size of 0.80 μm,
It was a monodispersed emulsion containing octahedral silver iodobromide grains with a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ossein gelatin

100.0 g

[0102]

[Chemical formula 18] 28% ammonia aqueous solution

440.0ml 56% acetic acid aqueous solution

With 660.0ml water


5000.0ml <H-1> Ossein gelatin

82.4 g potassium bromide

151.6 g potassium iodide

90.6 g Finish with water

1030.5ml <S-1> Silver nitrate

309.2 g 28% ammonia aqueous solution
Equivalent Finish with water
10
30.5ml <H-2> Ossein gelatin

302.1 g potassium bromide

770.0 g Potassium iodide

Finish with 33.2 g water

3776.8ml <S-2> Silver nitrate

1133.0 g 28% ammonia aqueous solution
Equivalent Finish with water
37
76.8ml

[0103] Using the same method as above, the average grain size, temperature, pAg, pH, flow rate, addition time and halide composition of the seed crystals were changed as appropriate, and the seed crystals were used for each layer having different average grain sizes and silver iodide contents. Each emulsion was prepared. All of these were core/shell type monodisperse emulsions with a distribution width of 20% or less.

Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and the sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7 -Tetrazaindene, 1-phenyl-5-mercaptotetrazole were added.

[0105] The above-mentioned photosensitive material sample 101 further contains compounds SU-1 and SU-2, a viscosity modifier, and a hardening agent H-
1, H-2, stabilizer ST-1, antifoggant AF-1,
AF-2 (weight average molecular weight 10,000 and 1,
100,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg/m2) as appropriate.

[0106]

[Chemical formula 19]

[0107]

[C20]

[0108]

[C21]

[0109]

[C22]

[0110]

[C23]

[0111]

[C24]

[0112]

[C25]

[0113]

[C26]

[0114]

[C27]

[0115]

[C28]

[0116] In addition, photosensitive material sample 102 was prepared in the same manner as above, except that the boron polymer of the present invention was added to the 11th layer, 12th layer, and 5th layer as shown in Table 1. ~107 were created respectively. Furthermore, photosensitive material sample 108 was prepared in the same manner as photosensitive material sample 101 except that the following compound was added to the protective layer in an amount of 5% by weight based on the amount of gelatin in the protective layer.

[0117]

embedded image Each of the obtained samples 101 to 108 was exposed to white light through a step wedge for sensitometry, and then developed under the following conditions.

[0118]

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and their replenisher were used.

Color developer water

800 ml potassium carbonate

30g
sodium hydrogen carbonate

2.5 g potassium sulfite

3.0 g sodium bromide

1.3 g potassium iodide

1.2 mg hydroxylamine sulfate

2.5 g sodium chloride

0.6 g 4-amino-
3-Methyl-N-ethyl-N-
4.5 g (β-hydroxylethyl)aniline sulfate diethylenetriaminepentaacetic acid

3.0 g potassium hydroxide

Add 1.2 g water and 1
liter and adjust the pH to 10.06 using potassium hydroxide or 20% sulfuric acid.

Color developer replenisher water

800 ml potassium carbonate

35g
sodium hydrogen carbonate

3 g potassium sulfite

5 g sodium bromide

0.4 g Hydroxylamine sulfate
3.1 g
4-amino-3-methyl-N-ethyl-N-
6.3 g (β-hydroxylethyl)aniline sulfate Potassium hydroxide
2g
diethylenetriaminepentaacetic acid
3.0
Add water to make 1 liter, add potassium hydroxide or
Adjust pH to 10.18 using 0% sulfuric acid.

Bleach solution water

700 ml 1,3 Diaminopropane Tetraacetate Iron(III) Ammonium
125 g ethylenediaminetetraacetic acid

2 g sodium nitrate

40 g ammonium bromide
150
g Glacial acetic acid

Add 40 g water to make 1 liter, and adjust the pH to 4.4 using aqueous ammonia or glacial acetic acid.

Bleach replenisher water

700 ml 1,3 Diaminopropane Tetraacetate Iron(III) Ammonium
175 g ethylenediaminetetraacetic acid

2 g sodium nitrate

50 g ammonium bromide
200
g Glacial acetic acid

After adjusting the pH to 4.0 using 56 g ammonia water or glacial acetic acid, add water to make 1 liter.

Fixer water

800 ml ammonium thiocyanate
120 g ammonium thiosulfate
150g
sodium sulfite

15 g ethylenediaminetetraacetic acid

p using 2 g aqueous ammonia or glacial acetic acid.
Add water after adjustment to H6.2 to make 1 liter.

Fixer replenisher water

800 ml ammonium thiocyanate
150 g ammonium thiosulfate
180g
sodium sulfite

20 g ethylenediaminetetraacetic acid

p using 2 g aqueous ammonia or glacial acetic acid.
After adjusting to H6.5, add water to make 1 liter.

Stabilizer and Stable Replenisher Water

900ml

[0127]

[Chemical formula 30] Dimethylol urea

0.5 g hexamethylenetetramine

0.2 g 1,2-benzisothiazolin-3-one
0.1 g siloxane (UCC L-77)

0.1 g ammonia water

After adding 0.5 ml water to make 1 liter, adjust the pH to 8.5 using aqueous ammonia or 50% sulfuric acid.

[0128] For each of Samples 101 to 108 after the development process, the antistatic performance and the photographic performance after the development process were evaluated in the following manner. The results are shown in Table 1.

[0129]

[Table 1] *1 Evaluation of antistatic performance (ash adhesion test) The side of the emulsion of the developed sample was rubbed several times with a rubber roller, cigarette ash was brought close, and whether or not it would stick to the film was examined according to the evaluation below. ○: No adhesion at all even if brought close to 1cm ○△: 1
It will stick if you bring it closer to 4cm~ △: 4cm~
Adheres when brought closer to 10 cm ×: Adheres even if it is closer than 10 cm ○ If it is △ or above, there is no practical problem.

*2 Photographic performance evaluation (storability) The prepared photosensitive materials and these were further heated at 40°C and 80% R. H. A preserved sample that had been forced to deteriorate by being left in an atmosphere for 7 days was prepared, and its relative sensitivity was examined by wedge exposure using an electrodeless discharge tube with main luminance in the range of 300 to 400 nm. For relative sensitivity, the sensitivity of a comparative sample not using boron polymer was set as 100.

As is clear from Table 1, Samples 102 to 107 using the boron polymer of the present invention are all excellent in both photographic performance and antistatic properties.

Example 2 One side (surface) of triacetyl cellulose film support
was subjected to subbing processing, and then, with the support sandwiched therebetween, layers having the following compositions were successively created from the support side on the opposite side (back side) to the surface subjected to the subbing processing.

[0133] Back side first layer Alumina sol AS-100 (aluminum oxide) 0.8 g
(Manufactured by Nissan Chemical Industries, Ltd.) Second layer on the back: Diacetyl cellulose

100 mg stearic acid

10 mg Silica fine particles (average particle size 0.2 μm)
Next, each layer having the composition shown in Photosensitive Material Prescription 2 below was sequentially formed from the support side on the undercoated surface of a triacetyl cellulose film support to prepare photosensitive material sample 201.

Photosensitive material formulation 2 First layer (antihalation layer) Black colloidal silver

0.24 g Ultraviolet absorber U-1

0.14 g Ultraviolet absorber U-2

0.072g UV absorber U-3
0.072g UV absorber U-4
0.07
2g High boiling point solvent Oil-1

0.31 g High boiling point solvent Oil-3

0.098g PolyN vinylpyrrolidone
0.15 g gelatin

2.02
g2nd layer (intermediate layer) High boiling point solvent Oil-2

0.011g gelatin

1.17 g Third layer (low sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-12 and S-13 (silver iodide 3.0 mol%, average grain size 0)
．． 30μm) 0
．． 60g coupler C-3

0.37 g High boiling point solvent Oil-
3
0.093g PolyN vinylpyrrolidone
0.074g gelatin

1.35 g 4th layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-12 and S-13 (silver iodide 3.0 mol%, average grain size 0)
．． 80μm) 0
．． 60g coupler C-3

0.85 g High boiling point solvent Oil-
3
0.21 g polyN vinylpyrrolidone
0.093g gelatin

1.56 g 5th layer (intermediate layer) Compound SC-1

0.20 g High boiling point solvent Oil-2

0.25 g Matting agent MA-
1
0.0091g gelatin
1.
35 g 6th layer (low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-14 (silver iodide 3.0 mol%, average grain size 0.30 μm)
) 0.70 g
Coupler M-1

0.31 g coupler M-3

0.076g High boiling point solvent Oi
l-2
0.059g poly-N
vinyl pyrrolidone
0.074g
gelatin

1.29 g 7th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-14 (silver iodide 3.0 mol%, average grain size 0.80 μm
) 0.70 g
Coupler M-1

0.80 g coupler M-3

0.19 g Compound AS-1

0.055g High boiling point solvent Oil-2
0.16
g PolyN vinylpyrrolidone
0
．． 12 g gelatin

1.91 g 8th layer (middle layer) gelatin

0.90 g 9th layer (yellow filter layer) Yellow colloidal silver

0.11 g Compound SC-1

0.068g High boiling point solvent Oi
l-2
0.085g Matting agent MA-1
0.012g
gelatin

0.68 g 10th layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-15 (silver iodide 3.0 mol%, average grain size 0.30 μm)
) 0.70 g
Coupler Y-2

0.86 g Image stabilizer G-1

0.012g High boiling point solvent Oil
-2
0.22 g polyN vinylpyrrolidone
0.078g Compound HS-2
0.
020g Compound HS-1

0.040g gelatin

1.09 g 11th layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-15 (silver iodide 3.0 mol%, average grain size 0.85 μm)
) 0.70 g
Coupler Y-2

1.24 g Image stabilizer G-1

0.017g High boiling point solvent Oil
-2
0.31 g PolyN vinylpyrrolidone
0.10 g Compound HS-2
0.
039g Compound HS-1

0.077g gelatin

1.73 g 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, average grain size 0.08 μm)
0.075g UV absorber U-1
0.048g
UV absorber U-2
0.0
24g UV absorber U-3

0.024g UV absorber U-4

0.024g high boiling point solvent Oil-1

0.13 g high boiling point solvent Oil-3

0.13 g compound HS-
2
0.075g compound HS-1
0.15
g gelatin

1.2 g 13th layer (protective layer-2) Compound A

0.041g Matting agent MA-2

0.0090g matting agent MA-3

0.051g Compound B

0.00
36g gelatin

0.55 g (Note: PolyN used in each layer
The weight average molecular weight of vinylpyrrolidone is 350,000. )

[0135] The above photosensitive material sample 201 further contains gelatin hardeners H-1, H-2, H-3, water-soluble dyes AI-1, AI-2, AI-3, compound DI-1, and stable Agent ST-1 and antifoggant AF-1 were added as appropriate.

The silver halide emulsions used in each photosensitive layer were all monodisperse emulsions with a distribution width of 20% or less.

After desalting and washing with water, each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and each sensitizing dye and 4-hydroxy for spectral sensitization. -6-methyl-1,3,3a
, 7-tetrazaindene, and 1-phenyl-5-mercaptotetrazole were added. In addition, .

[0138]

[Chemical formula 31]

[0139]

[C32]

[0140]

[Chemical formula 33]

[0141] In addition, the above photosensitive material sample 201 was prepared in the same manner except that the boron polymer of the present invention was added to the 5th layer, 12th layer and 13th layer as shown in Table 2.
Photosensitive material samples 202 to 207 were prepared, respectively. Furthermore, photosensitive material sample 208 was prepared in the same manner as photosensitive material sample 201 except that the following compound was added to the protective layer in an amount of 5% by weight based on the amount of gelatin in the protective layer.

[0142]

embedded image Each of the obtained samples 201 to 208 was exposed to white light through a step wedge for sensitometric measurement, and then subjected to the following development treatment.

Processing process Processing time Processing temperature First development 6 minutes
Wash with water at 38℃
2 minutes 38℃ inversion
2 minutes 38℃
Color development 6 minutes
38℃ adjustment 2 minutes
38℃ bleaching
6 minutes 38℃ constant
Arrive 4 minutes
Wash with water at 38℃ for 4 minutes
Stable at 38℃
1 minute dry at room temperature
The composition of the treatment liquid used in the drying step is as follows.

First developer Sodium tetrapolyphosphate
2 g
sodium sulfite

20 g hydroquinone monosulfonate
30g
Sodium carbonate (monohydrate)
30g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone

2 g potassium bromide

2.5g potassium thiocyanate

1.2g potassium iodide (0.1% solution)
Add 2 ml water to pH 9.60
, the volume was increased to 1000ml.

Reversal solution Nitrilotrimethylenephosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate)
1 g p-aminophenol
0.1g sodium hydroxide
8 g glacial acetic acid

Add 15 ml water, pH 5.75, 1000m
I set it to l.

Color developer Sodium tetrapolyphosphate
3g
sodium sulfite

7 g Sodium phosphate (dihydrate)
36
g potassium bromide

1 g potassium iodide (0.1% solution)

90 ml sodium hydroxide

3 g citradinic acid

1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-aminoaniline sulfate
11 g 2,2-ethylene dithiodiethanol
Add 1 g water, pH 11.7
The volume was raised to 0.1000ml.

Adjustment liquid Sodium sulfite

12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin
0.4 m
l Glacial acetic acid

Add to 3 ml water, pH 6.15,1
The volume was raised to 000ml.

Bleach solution Sodium ethylenediaminetetraacetate (dihydrate)
2 g Ethylenediaminetetraacetic acid iron(III) ammonium (dihydrate) 12
0 g ammonium bromide

Add 100g water, pH 5.65, 1000m
I set it to l.

Fixer ammonium thiosulfate
80
g Sodium sulfite

5 g sodium bisulfite

Add 5 g water to pH 6.60,100
I raised it to 0ml.

Stabilizing liquid Formalin (37% by weight)
5
ml Konidax (manufactured by Konica Corporation)
5ml
Water was added to adjust the pH to 7.00 and 1000 ml.

[0151] Each of Samples 201 to 208 after the development process was evaluated for antistatic performance and photographic performance after the development process in the same manner as in Example 1. The results are shown in Table 2. However, relative sensitivity was expressed with comparative sample 201 as 100.

[0152]

[Table 2] As is clear from Table 2, samples 202 to 207 using the boron polymer of the present invention are all excellent in both photographic performance and antistatic properties.

Example 3 Both sides of a polyethylene terephthalate film with a thickness of 100 μm after biaxial stretching and heat setting were subjected to corona discharge treatment at 8 W/m2·min, and on one side, the following undercoat coating liquid B-3 was applied.
The undercoat layer B-3 was coated to a dry film thickness of 0.8 μm, and the following undercoat coating liquid B-4 was applied to the opposite side of the polyethylene terephthalate film from the undercoat layer B-3 to a dry film thickness of 0.8 μm. The undercoat layer B-4 was coated to a thickness of 0.8 μm.

Undercoat coating liquid B-3 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate.
Copolymer latex liquid (30% solids)
270g
Compound (C-6)

0.6 g Hexamethylene-1,6-bis(ethyleneurea) 0.8
g Make up to 1 liter with water.

Undercoat coating liquid B-4 Butyl acrylate 40% by weight, styrene 20%
Copolymer latex liquid of 40% by weight and glycidyl acrylate (solid content 30%) 270
g Compound (C-6)

0.6 g hexamethylene-1,
6-bis(ethyleneurea)
Make up to 1 liter with 0.8 g water.

Furthermore, subbing layer B-3 and subbing layer B-4
A corona discharge of 8 W/m 2 ·min was applied on each layer, and coating liquid B-5 below was applied on each layer to a dry film thickness of 0.1 μm.

Coating liquid B-5 Gelatin
10 g compound (C
-6)
0.2 g compound (C-7)
0.2
g compound (C-8)
0.1 g average particle size 3 μm
silica particles
Make up to 1 liter with 0.1 g water.

[0158]

[C35]

[0159] 25W was added to the subbing layer B-5 on both sides obtained above.
/m2・min of corona discharge, and furthermore, the above B-4, B
- On top of the subbing layer consisting of 5, apply the following backing layer coating solution B.
-1 to form a backing layer (applied gelatin amount 2.0g/
m2), and a backing protective layer (coated gelatin amount 1.5 g/m2) using backing layer protective film layer coating liquid B-2.
and an emulsion layer (coated gelatin amount: 2.0 g/m2) and an emulsion protective layer (coated) using the following silver halide photosensitive material coating solution formulation 3 on the undercoat layer consisting of A light-sensitive material sample 301 was prepared by simultaneously coating four layers of gelatin (1.0 g/m2) and drying.

(Preparation of coating solution B-1 for backing layer) After swelling 36 g of gelatin in water and dissolving it by heating, 1.6 g of compound (C-1), 310 mg of (C-2) as dyes,
(C-3) 1.9 g and compound (N) 2.9 g were added as an aqueous solution, then 11 ml of a 20% saponin aqueous solution,
5 g of Compound (C-4) was added as a physical property modifier, and then a methanol solution of 63 mg of Compound (C-5) was added. The viscosity was adjusted by adding 800 g of a water-soluble thickener styrene-maleic acid copolymer to this liquid, and the pH was further adjusted to 5.4 using an aqueous citric acid solution, resulting in a reaction product of polyglycerol and epichlorohydrin: 1.5 g. , add 144mg of glyoxal, and add water to make 960ml.
A backing layer coating liquid B-1 was prepared.

[0161]

[C36]

[0162]

[C37]

(Coating liquid B-2 for protective film layer of backing layer)
Preparation) Swell 50 g of gelatin in water, heat and dissolve, and then
-sulfonate-bis(2-ethylhexyl) succinate
340 mg of ester sodium salt, 3.4 g of sodium chloride, 1.1 g of glyoxal, and 540 mg of mucochloric acid were added. To this, spherical polymethyl methacrylate with an average particle size of 4 μm was added as a matting agent.
It was added to give a concentration of 0 mg/m2, and water was added to make up the total volume to 1 liter to prepare a protective film layer coating liquid B-2.

Photosensitive material formulation 3 Preparation of silver halide emulsion coating solution After adding 9 mg of compound (A) to the following emulsion, the pH was adjusted to 6.5 using 0.5N sodium hydroxide solution, and then compound (A) was added to the emulsion shown below. Add 360 mg of T), and further add 5 ml of 20% saponin aqueous solution per mole of silver halide, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, and 43 ml of the following latex for emulsion addition (L) to form a compound. (M) 60m
g, and 280 mg of a styrene-maleic acid copolymer water-soluble polymer as a thickener were sequentially added, and 475 m of water was added.
A silver halide emulsion coating solution was prepared.

(Preparation of emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as follows.

23.9 mg of pentabromorodium potassium salt per 60 g of silver nitrate, an aqueous solution containing sodium chloride and potassium bromide, and an aqueous silver nitrate solution were simultaneously mixed in an aqueous gelatin solution at 40° C. for 25 minutes with stirring. A silver chlorobromide emulsion with an average grain size of 0.20 μm was prepared.

6-Methyl-4- as a stabilizer was added to this emulsion.
Hydroxy-1,3,3a,7-tetrazaindene 2
After adding 00 mg, the mixture was washed with water and desalted.

After adding 20 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene, sulfur sensitization was carried out. After sulfur sensitization, gelatin was added and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.
,7-tetrazaindene and then diluted with water to 26
An emulsion was prepared by finishing the volume to 0 ml.

(Preparation of latex (L) for emulsion addition) 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Meito Sangyo and 0.05 kg of ammonium persulfate were added to 40 liters of water at a liquid temperature of 81°C. While stirring and under nitrogen atmosphere, n-butyl acrylate 4.5
1kg, styrene 5.49kg and acrylic acid 0.1k
g of the mixed solution was added over 1 hour, and then 0.005 kg of ammonium persulfate was added, and after further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 using aqueous ammonia.

[0170] The obtained latex liquid was filtered using a GF/D filter manufactured by Whoman, and made up to 50.5 kg with water to obtain a monodisperse latex (L) with an average particle size of 0.25 μm.
It was created.

(Preparation of coating solution for emulsion protective film) Water was added to gelatin, and after swelling, it was dissolved at 40°C, and then a 1% aqueous solution of compound (Z) as a coating aid, compound (N) as a filter dye, and Compound (D) was added one after another, and the pH was further adjusted to 6.0 with citric acid solution. A matting agent (amorphous silica with a particle size of 4.0 μm) was added to prepare a coating solution for an emulsion protective film.

[0172]

[C38]

[0173]

[C39]

In addition, Samples 302 to 310 were prepared in the same manner as Sample 301, except that the boron polymer of the present invention was added to the emulsion layer as shown in Table 3. Samples 311 and 312 were prepared in the same manner except that the boron polymer of the invention was added to the emulsion protective layer as shown in Table 3, and Sample 301 was prepared by adding the boron polymer of the invention to the backing layer as shown in Table 3. Samples 313 were prepared in the same manner except for the addition. Furthermore, photosensitive material sample 314 was prepared in the same manner as photosensitive material sample 301 except that the following compound was added to the emulsion protective layer in an amount of 5% by weight based on the amount of gelatin in the protective layer.

[0175]

[C40]

Each of the obtained samples 301 to 314 was exposed to white light through a step wedge for sensitometric measurement, and then subjected to the following treatment. (Processing conditions) Process Temperature (°C) Time (seconds) Development 34
15 fixed
34 15 Washing with water
At normal temperature
10 drying 40
9

[Developer formulation] (Composition A) Water

150ml Ethylenediaminetetraacetic acid disodium salt 2g
diethylene glycol
50g
Potassium sulfite (55% W/V aqueous solution)
100ml potassium carbonate
50 g hydroquinone
15g
5-methylbenzotriazole
200mg 1-phenyl-5-mercaptotetrazole
30mg potassium hydroxide
Amount to adjust the pH of the solution to 10.9 Potassium bromide
4.
5 g (composition B) water

3ml diethylene glycol

50 g Ethylenediaminetetraacetic acid disodium salt 25 mg
Acetic acid (90% W/W aqueous solution)
0.3ml
5-nitroindazole
110mg 1
-phenyl-3-pyrazolidone
When using 500 mg developer, dissolve the above composition A and composition B in 500 ml of water in this order,
It was used after adding water to make up to 1 liter.

[Fixer formulation] (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution)
230ml sodium sulfite
9.5 g Sodium acetate trihydrate
15.9 g boric acid

6.7 g Sodium citrate dihydrate
2 g acetic acid (90% W/
W aqueous solution)
8.1ml (composition B) water

17ml sulfuric acid (50% W/W aqueous solution)

5.8 g aluminum sulfate (aqueous solution with Al2O3 equivalent content of 8.1% W/W)
26.5 g

[0179]
When using a fixer, add the above composition A and composition B in 500 ml of water.
Dissolved in this order, added water to make up to 1 liter, and used. The pH of this fixer was about 4.3.

[0180] The above %W/W represents (% weight)/(weight), and %W/V represents (% weight)/(volume).

[0181] For each of Samples 301 to 314 after the development process, the antistatic performance and the photographic performance after the development process were evaluated in the same manner as in Example 1. The results are shown in Table 3. However, relative sensitivity was expressed with comparative sample 301 as 100.

[0182]

[Table 3] As is clear from Table 3, the boron polymer of the present invention not only has excellent antistatic performance, but also has excellent photographic performance.
No adverse effects.

Example 4 Both sides of a 100 μm thick polyethylene terephthalate film after biaxial stretching and heat setting were subjected to a corona discharge treatment of 8 W/m2·min, and the following undercoat coating liquid B-3 was dried on one side. The undercoat layer B-3 was coated to a film thickness of 0.8 μm, and the following undercoat coating liquid B-4 was applied to the opposite side of the polyethylene terephthalate film from the undercoat layer B-3 to a dry film thickness of 0. The undercoat layer B-4 was coated to a thickness of .8 μm.

Undercoat coating liquid B-3 Copolymer latex liquid of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate (solid content 30%)

270 g Compound (C-6)
0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Make up to 1 liter with water.

Undercoat coating liquid B-4 Butyl acrylate 40% by weight, styrene 20%
Copolymer latex liquid of 40% by weight and glycidyl acrylate (solid content 30%)

270 g Compound (C-6)
0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Make up to 1 liter with water.

[0186] Furthermore, the above subbing layer B-3 and subbing layer B
-4 was subjected to a corona discharge of 8 W/cm 2 ·min, and the following coating liquid B-5 was coated to a dry film thickness of 0.05 μm.

[0187]

[C41] Add water to make 1 liter.

On both sides of this undercoated polyethylene terephthalate film support, each layer having the composition shown in Photosensitive Material Prescription 4 below was sequentially formed from the support side after corona discharge to prepare photosensitive material sample 401.

Photosensitive material formulation 4 Silver iodide 2 with an average grain size of 0.3 μm was processed by the double jet method at 60° C., pAg=8, and pH=2.0.
A monodisperse cubic emulsion (A) of silver iodobromide containing mol % was obtained. In this emulsion, the incidence of twin crystals was 1% or less in terms of number as determined by electron micrographs. Using this emulsion (A) as a seed crystal, it was grown as follows.

That is, this seed crystal (A) was dissolved in 8.5 liters of a solution containing protected gelatin and optionally ammonia kept at 40° C., and the pH was further adjusted with acetic acid. Using this liquid as a mother liquid, a 3.2N aqueous ammoniacal silver ion solution was added by a double jet method. In this case, the pH
and EAg were changed as needed depending on the silver iodide content and crystal habit. In other words, pAg is controlled to 7.3, pH is controlled to 9.7,
A layer containing 35 mol % of silver iodide was formed. Next, to 95% of the particle size, the pH was changed from 9 to 8 and the pAg was changed to 9.
It was kept at 0 and allowed to grow. Thereafter, a potassium bromide solution was added using a nozzle over a period of 8 minutes to reduce the pAg to 11.0, and the mixing was completed 3 minutes after the addition of potassium bromide was completed. This emulsion is
The average grain size is 0.55 μm, and the silver iodide content of the entire grain is about 2.2 mol%.

Next, a desalting step was performed to remove excess soluble salts from this reaction solution. That is, the reaction solution was kept at 40°C, and the following compound (I) 5g/AgX1 mol, MgSO
48 g/1 mole of AgX was added, stirred for 5 minutes, and then left to stand. Thereafter, the supernatant liquid was discharged to make a liquid volume of 200 cc per mole of AgX. Next, add 1 liter of pure water at 40°C.
．． 8 liters/1 mole of AgX was added and stirred for 5 minutes. Next, 20 g of MgSO4/1 mol of AgX was added, the mixture was stirred and allowed to stand in the same manner as above, and the supernatant liquid was removed to perform desalting. The solution was then stirred and post-gelatin was added to redisperse the AgX.

The obtained emulsion was subjected to chemical sensitization as follows. That is, first, the emulsion was kept at 55°C. Thereafter, ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold/sulfur sensitization. After sensitization, 4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene was added.

In the above steps, a sensitizing dye was added at the end of each step.

AgX1 was added to these emulsions as an additive.
Per mole: 400 mg of t-butyl-catechol, 1.0 g of polyvinylpyrrolidone (molecular weight 10,000), 2.5 g of styrene/maleic anhydride copolymer, 10 g of trimethylolpropane, 5 g of diethylene glycol, nitrophenyl-triphenylphosphonium chloride. 5
0mg, ammonium 1,3-dihydroxybenzene-4-sulfonate 4g, sodium 2-mercaptobenzimidazole-5-sulfonate 15mg

[0195]

embedded image 10 mg of 1,1-dimethylol-1-bromo-1-nitromethane was added to prepare an emulsion coating solution.

The following compounds were also added as protective layer additives. (The amount added is shown per 1 g of gelatin.)

[
0197]

[C43]

[0198] Furthermore, 7 mg of a matting agent made of polymethyl methacrylate with an average particle size of 5 μm, and an average particle size of 0.013 μm.
m colloidal silica 70mg, (CHO) 28mg,
6 mg of HCHO was added to prepare a coating solution for a protective layer.

[0199] The amount of coated silver for each sample was 5 g/m2 on both sides.
The coating solution for the protective layer was a 3% gelatin solution, and the amount of gelatin coated on both sides, including the emulsion layer protective layer, was 6.5 g/m2.
It was applied so that it became 2.

[0200]

[C44]

[0201] In addition, in preparing the above-mentioned photosensitive material sample 401, the same procedure was followed except that the boron polymer of the present invention was added to the protective layer as shown in Table 4, and the above-mentioned protective layer additives (2) and (4) were omitted. Photosensitive material samples 402 to 407 were prepared respectively.

[0202] For each of the obtained samples 401 to 407, standard light B described in the "New Edition, Lighting Data Book" was used as the light source, and an exposure time of 0.1 seconds and 3.2 cm was applied to both sides of the film without a filter. They were exposed to the same amount of light. The above sample was processed for 45 seconds with an XD-SR developer using an SRX-501 automatic processor (manufactured by Konica Corporation).

[0203] Each of Samples 401 to 407 after the development process was evaluated for antistatic performance and photographic performance after the development process in the same manner as in Example 1. The results are shown in Table 4.

[0204]

Table 4 As is clear from Table 4, all samples 402 to 407 using the boron polymer of the present invention are excellent in both photographic performance and antistatic properties.

Example 5 Corona discharge treatment was applied to both sides of a biaxially stretched polyethylene terephthalate having a thickness of 100 μm at 8 W/m 2 ·min. Furthermore, 20 ml/m2 of the following coating solution for the first undercoat layer containing the boron polymer of the present invention in the amount shown in Table 5 was applied.
It was coated so as to have the following properties and dried at 100° C. for 3 minutes to prepare subbed samples 501 to 511, respectively.

Coating liquid for first layer (1) Water-dispersed polyester (Eastman AQ2
9D solid content 30%) (Manufactured by Eastman Kodak Company)
12.3 g 2,4-dichloro-6-hydroxy-S-triazine 3.7 g α
-Sulfosuccinic acid di(2-ethylhexyl) ester sodium salt
0.2 g
Boron polymer of the present invention
Table 5 Pure water
83.
8 g 1st layer coating liquid (2) Water-dispersed latex (vinylidene chloride/methyl acrylate/acrylic acid = 90/5/5)
1
7 g boron polymer of the present invention
Table 5 Pure water

83 g 1st layer coating liquid (3) Water-dispersed latex (glycidyl methacrylate/
Butyl acrylate/styrene = 30/50/2
0 solid content 30%) 10 g
The following anionic surfactant (C-6)
20mg hexamethylene-1,6-bis(ethyleneurea)
30mg boron polymer of the present invention

Table 5 Pure water

90 g 1st layer coating liquid (4) Water-dispersed latex (2-hydroxyethyl methacrylate/butyl acrylate/acrylic acid-
t-butyl/styrene =25/30/25/3
0 solid content 30%)
10 g Anionic surfactant (C-6)
20mg Hexamethylene-1,6-bis(ethyleneurea) 30mg
Boron polymer of the present invention
Table 5 Pure water
9
0 g 1st layer coating liquid (5) Water-dispersed latex (butadiene/styrene/acrylic acid = 66/33/1)

10 g 2,4-dichloro-hydroxy-S-triazine sodium salt

1
6mg boron polymer of the present invention
Table 5 Pure water

90 g of the above first undercoat layer was subjected to corona discharge treatment at 8 W/m2・min, and 2 coats of the following second undercoat layer coating solution were applied.
After coating at a film thickness of 0 ml/m2, it was dried at 100°C for 1 minute.

Gelatin
1 g saponin
20mg pure water
Each of subbed-processed polyethylene terephthalate samples 501 to 511 prepared using 100 g or more was sandwiched with a coating solution having the composition of multilayer photographic light-sensitive material formulation 1 used in Example 1 and a support, and on the opposite side was coated with the following gelatin. Multilayer photographic material samples 501 to 511 were prepared by forming each layer of the laminated composition (BC).
were prepared respectively.

[0208] As the first layer of the gelatin layered composition (BC), liquid A: di-n-octyl phthalate.
2g
Ethyl acetate

1 g liquid B gelatin

1 g Sodium triisopropylnaphthalene sulfonate 2 g
Pure water

19 g After dispersing solution A in solution B, add gelatin to this solution.

3.5 g pure water

46.5 g of aqueous solution was added. After that, the volume was made up to 80 ml with pure water.

2-dihydroxy 4,6-dichloro-S-triazine sodium salt

15mg Sodium p-dodecylbenzenesulfonate 10mg
was applied to a film thickness of 60 μm and heated at 100°C for 1
Let dry for a minute. Gelatin as the second layer

4.5 g pure water

57 g 2-dichloro-S-triazine sodium salt
Apply 15 mg to a film thickness of 50 μm,
It was dried at 0°C for 1 minute. As the third layer, gelatin

4.5 g pure water

57 g 2-dichloro-S-triazine sodium salt
15mg Matting agent (0.25μ particles of polymethyl methacrylate) 0.6g to 1
It was applied to a film thickness of 0 μm and dried at 100° C. for 1 minute.

[0210] Each of the obtained samples 501 to 511 was exposed to light in the same manner as in Example 1, and the relative sensitivity and haze test and surface resistivity of the obtained samples were measured by the following methods. The results are shown in Table 5. Note that the relative sensitivity is expressed with comparative sample 510 as 100.

[0211] Haze test After coating the multilayer photographic light-sensitive layer, the sample was developed without exposure to light using a turbidity meter Model T-2600 manufactured by Tokyo Denshoku Co., Ltd.
The haze was measured using DA and expressed in %.

[0212] Surface resistivity: Using a terra ohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd., an applied voltage of 100 V, 23°C, 20% R. H. Measured under the following conditions.

[0213]

[Table 5]

Example 6 Example 2 was added to each of the undercoated polyethylene terephthalate samples 501 to 511 prepared in the same manner as in Example 5.
A multilayer photographic light-sensitive material was prepared by forming a gelatin laminated composition (BC) similar to that used in Example 5 on the opposite side with the coating solution having the composition of multilayer photographic light-sensitive material formulation 2 used in Example 5 and the support sandwiched therebetween. Samples 601 to 611 were prepared, respectively.

[0215] Each of the obtained samples 601 to 611 was exposed to light in the same manner as in Example 2, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 6. In addition, the relative sensitivity is 1 for comparison sample 610.
Expressed as 00.

[0216]

[Table 6]

Example 7 Backing layer coating liquid B-1 prepared in the same manner as in Example 3 was applied to each of the undercoated polyethylene terephthalate samples 501 to 511 prepared in the same manner as in Example 5. and B-2, which is a coating liquid for the protective layer, were applied in this order. Further, on the opposite side, a silver halide emulsion coating liquid having the composition of photosensitive material formulation 3 used in Example 3 and its protective layer composition liquid were sequentially applied to form photosensitive material sample 701.
~711 were created respectively.

[0218] Each of the obtained samples 701 to 711 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 7. In addition, the relative sensitivity is 1 for comparison sample 710.
Expressed as 00.

[0219]

[Table 7]

Example 8 Each of the undercoated polyethylene terephthalate samples 501 to 511 prepared in the same manner as in Example 5 was coated with a silver halide emulsion coating solution having the composition of photosensitive material formulation 4 used in Example 4 and its protection. The layer composition liquid was sequentially applied to both sides to prepare photosensitive material samples 801 to 811, respectively.

[0221] Each of the obtained samples 801 to 811 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 8. In addition, the relative sensitivity is 1 for comparison sample 810.
Expressed as 00.

[0222]

[Table 8] As is clear from each of Examples 5 to 8, excellent antistatic performance can be obtained by containing the boron polymer of the present invention in the underlayer without adversely affecting photographic performance.

Example 9 Both sides of a 100 μm thick polyethylene terephthalate film after biaxial stretching and heat setting were subjected to a corona discharge treatment of 8 W/m2·min, and one side was coated with a subbing coating similar to that used in Example 4. Liquid B-3 was used as the undercoat layer B-3 to have a dry film thickness of 0.8 μm, and the same undercoat as used in Example 4 was applied to the opposite side of the undercoat layer B-3 with the polyethylene terephthalate film in between. Coating liquid B-4 was applied as subbing layer B-4 so that the dry film thickness was 0.8 μm.

Further, a corona discharge of 8 W/m2·min was applied to the undercoat layer B-3, and the following coating solution B-6 was applied to a dry film thickness of 0.1.
It was coated as a subbing layer B-6 so that the thickness was .mu.m.

Coating liquid B-6 Gelatin
10 g compound (C-6)
0.2 g compound (C-7)
0.2 g compound (C-8)
Add 0.1 g of silica particles with an average particle size of 3 μm and 0.1 g of water to make up to 1 liter.

Further, on the undercoat layer B-4, a corona discharge of 8 W/m2·min was applied, and an antistatic layer containing the boron compound of the present invention described below was formed.

Antistatic Layer-1 A coating solution in which the boron polymer of the present invention was dispersed in the coating solution B-7 below in an amount shown in Table 9 was coated with a dry film thickness of 0.8 μm.
It was coated as a subbing layer B-7 so as to have a thickness of m.

Coating liquid B-7 Water-soluble conductive polymer (C-9)
60
g Latex liquid containing compound (C-10) (solid content 20%) 80 g Ammonium sulfate
0.5g
Hardening agent (C-11)

12 g polyethylene glycol (
Weight average molecular weight 600)
Make up to 1 liter with 6 g water.

Antistatic Layer-2 A coating solution prepared by dispersing the boron polymer of the present invention in the coating solution B-8 below in an amount shown in Table 9 was applied to a coating solution with a dry film thickness of 0.8 μm.
The undercoat layer B-8 was coated so that the thickness of

Conductive polymer (styrene sulfonic acid sodium salt/maleic acid = 3:1) (Compound C-9) Latex liquid (43% styrene, 45% butyl methacrylate, 4% butyl acrylate, 8% methacrylic acid) Polyfunctional Contains functional aziridine (described below) in a weight ratio of conductive polymer/latex/polyfunctional aziridine = 60/40/15.

[0231]

[C45]

A corona discharge of 25 W/m2·min was applied to the undercoat layer B-6 obtained as described above, and a corona discharge of 8W/m2·min was applied to the undercoat layer B-7 or B-8. A corona discharge of 10 minutes was applied.

Furthermore, coating liquid B- for backing layer similar to that used in Example 3 was applied on subbing layer B-7 or B-8.
A backing layer (applied gelatin amount 2.0 g/m
2) and a backing protective layer (coated gelatin amount 1.5 g/m2) using coating liquid B-2 for protective film layer, and
On the subbing layer B-6, an emulsion layer (
An emulsion protective layer (coated gelatin amount: 1.0 g/m2) and a coating solution for emulsion layer protective film were used.
2) was applied in four layers at the same time and dried to prepare photosensitive material samples 901 to 910, respectively.

[0234] Each of the obtained samples 901 to 910 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 9. In addition, the relative sensitivity is 1 for comparison sample 908.
Expressed as 00.

[0235]

[Table 9]

Example 10 Corona discharge was applied to both sides of a biaxially stretched polyethylene terephthalate film with a thickness of 100 μm at 8 W/m2·min, and the following coating solution for the first sublayer was applied at a concentration of 20 ml/m2. It was coated on both sides and dried at 100°C for 3 minutes.

Coating liquid for first layer (1) Water-dispersed latex (2-hydroxyethyl methacrylate/butyl acrylate/acrylic acid)
t-butyl/styrene =25/30/25/2
0 solid content 30%)
10 g Anionic surfactant (C-6)
20mg hexamethylene-1,6
-Bis(ethylene urea) 30mg
Pure water

90 g 1st layer coating liquid (2) Water-dispersed latex (butadiene/styrene/acrylic acid = 66/33/1)

10 g 2,4-dichloro-hydroxy-S-triazine sodium salt


16mg pure water

90 g 1st layer coating liquid (
3) Water-dispersed latex (vinylidene chloride/methyl acrylate/acrylic acid = 90/5/5)

17 g pure water

83 g 1st layer coating liquid (4
) Water-dispersed latex (glycidyl methacrylate/
Butyl acrylate/styrene = 30/50/2
0 solid content 30%) 10
g Anionic surfactant (C-6)
20mg
Hexamethylene-1,6-bis(ethyleneurea)
30mg pure water

90g

02
38] Further, a corona discharge of 8 W/m2·min was applied to the first undercoat layer, and the boron polymer of the present invention was dispersed in the coating solution for the second undercoat layer in the amount shown in Table 10. The liquid was applied so that the dry film thickness was 0.8 μm.

[0239] Coating liquid gelatin for second layer of undercoat
10 g Compound (C-6) 0
．． 2 g Compound (C-7) 0
．． 3 g Compound (C-8) 0
．． 1 g Silica particles with an average particle size of 3 μm 0.1 g
Make up to 1 liter with water.

[0240] After applying a corona discharge of 8 W/m2·min to one side of the subbed support obtained as described above, coating liquid B-1 for backing layer similar to that used in Example 3 was applied. Using the backing layer (coated gelatin amount 2.0 g/m2) and protective layer coating liquid B-2, coat the backing protective layer (coated gelatin amount 1.5 g/m2) on the other side with 25W
After applying a corona discharge of /m2·min, an emulsion layer (coated gelatin amount: 2.0 g/m2) and an emulsion protective film were coated using a silver halide emulsion coating solution having the composition of photosensitive material formulation 3 used in Example 3. The emulsion protective layer (coated gelatin amount: 1.
Photosensitive material samples 1001 to 1016 were prepared by simultaneously coating four layers of 0g/m2) and drying them.

[0241] Each of the obtained samples 1001 to 1016 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 10. Note that the relative sensitivity is expressed with comparative sample 1012 as 100.

[0242]

[Table 10]

Example 11 A coating solution having the composition of multilayer photographic material formulation 1 used in Example 1 was applied to one side of a subbed support obtained in the same manner as in Example 10, and the support was sandwiched between the two sides. A gelatin laminated composition (BC) similar to that used in Example 5 was coated on the opposite side to prepare photosensitive material samples 1101 to 1116, respectively.

[0244] Each of the obtained samples 1101 to 1116 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 11. Note that the relative sensitivity is expressed with comparative sample 1112 as 100.

[0245]

[Table 11]

Example 12 A coating solution having the composition of the multilayer photographic material formulation 4 used in Example 4 was coated on both sides of the subbed support obtained in the same manner as in Example 10, and photosensitive material samples 1201 to 1216 was created.

[0247] Each of the obtained samples 1201 to 1216 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 12. Note that the relative sensitivity is expressed with comparative sample 1212 as 100.

[0248]

[Table 12]

Example 13 Corona discharge was applied to both sides of a biaxially stretched polyethylene terephthalate film with a thickness of 175 μm at 8 W/m2·min, and the following coating solution was applied to both sides with a film thickness of 20 μm, and then heated at 100° C. Dry in minutes.

Coating liquid Water dispersion latex (2-hydroxyethyl methacrylate/butyl acrylate/acrylic acid)
t-butyl/styrene) =25/30/25/
20 Solid content 30%
10 g Anionic surfactant (C-6)
20mg hexamethylene-1
,6-bis(ethyleneurea) 30m
g Pure water

90g

Further, a coating solution prepared by dispersing the boron polymer of the present invention in the amount shown in Table 13 in the coating solution shown below was coated to a dry film thickness of 0.1 μm.

[0252] Coating liquid water-soluble polymer compound (C-12)
5 g compound (C-6)
0.2 g compound (C-8)
0.2 g Silica particles with an average particle size of 3 μm 0.1
g Make up to 1 liter with water.

0253]

[C46]

[0254] After subjecting both surfaces of the obtained undercoated polyethylene terephthalate to a corona discharge treatment of 16 W/m2·min, a photographic constituent layer was applied using a coating solution having the composition of the multilayer photographic material formulation 1 used in Example 1. A back coat layer was coated on the other side using the same gelatin laminated composition (BC) used in Example 5, and photosensitive material samples 1301 to 1306 were prepared.
were created respectively.

[0255] Each of the obtained samples 1301 to 1306 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 13. Note that the relative sensitivity is expressed with comparative sample 1305 as 100.

0256]

[Table 13]

Example 14 Corona discharge was applied to both sides of a biaxially stretched polyethylene terephthalate film with a thickness of 100 μm at 8 W/m2·min, and the following coating solution was applied to both sides with a film thickness of 20 μm. Dry in minutes.

Coating liquid Water dispersion latex (2-hydroxyethyl methacrylate/butyl acrylate/acrylic acid)
t-butyl/styrene) =25/30/25/
20 Solid content 30%
10 g Anionic surfactant (C-6)
20mg hexamethylene-1
,6-bis(ethyleneurea) 30m
g Pure water

90g

Further, a coating solution prepared by dispersing the boron polymer of the present invention in the amount shown in Table 14 in the following coating solution was coated to a dry film thickness of 0.1 μm.

Coating liquid water-soluble polymer compound (C-12)
5 g compound (C-7)
0.2 g compound (C-8)
0.2 g
Silica particles with an average particle size of 3 μm
Make up to 1 liter with 0.1 g water.

[0261] After applying a corona discharge treatment of 16 W/m2·min to both surfaces of the obtained undercoated polyethylene terephthalate, one side was coated with a coating solution having the composition of multilayer photosensitive material formulation 4 used in Example 4. Emulsion layers were coated on both sides to prepare photosensitive material samples 1401 to 1406, respectively.

[0262] Each of the obtained samples 1401 to 1406 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 14. Note that the relative sensitivity is expressed with comparative sample 1405 as 100.

0263

[Table 14] As is clear from each of Examples 9 to 14, the samples in which the boron polymer of the present invention was added to the underlayer upper layer had almost no effect on photographic performance and were excellent in both conductivity and haze.

Example 15 Subbing treatment-1 Polyethylene terephthalate with an intrinsic viscosity of 0.65 dl/g was melted and extruded into a film at 280°C from a T-die, electrostatically applied, and rapidly cooled on a cooling drum at about 30°C. The unstretched film (thickness 1000 μm) obtained by
Coating solutions 1 to 8 having the compositions shown in Table 15 below were applied to a support that had been preheated and longitudinally stretched (3 times), then subjected to corona discharge treatment and surface treated.
was applied on both sides, dried and preheated in a tenter, stretched horizontally (3 times) at 100°C, and then heat-set at 220°C.
After cooling, a subbed-treated biaxially stretched polyethylene terephthalate film having a film thickness of 0.3 g/m2 (in terms of polymer) was obtained.

0265]

[Table 15]

[0266] Subbing treatment-2 Furthermore, 8W/
A coating solution having the following composition was applied to a support having a dry film thickness of 0.1 μm on a support that had been subjected to a corona discharge treatment of m2·min.

0267]

0268

[C47]

A photographic layer was provided on one side of the polyester film support after the subbing layer was coated using a coating solution having the composition of the multilayer photographic material formulation 3 used in Example 3. Further, a backing layer was provided on the side opposite to the photographic layer using the backing layer coating solution B-1 used in Example 13, and photosensitive material samples 1501 to 1508 were applied to each of the lower layer coating solutions 1 to 8, respectively. Created.

[0270] Each of the obtained samples 1501 to 1508 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 16. Note that the relative sensitivity is expressed with comparative sample 1501 as 100.

0271]

[Table 16]

Example 16 Photographic layers were provided on both sides of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 15 using a coating solution having the composition of multilayer photographic material formulation 4 used in Example 4. Photosensitive material samples 1601 corresponding to each of the underlayer coating solutions 1 to 8
~1608 was created.

[0273] Each of the obtained samples 1601 to 1608 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 17. Note that the relative sensitivity is expressed with comparative sample 1601 as 100.

0274]

[Table 17]

Example 17 A photographic layer was provided on one side of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 15 after coating the composition of the multilayer photographic material formulation 1 used in Example 1. Ta. Further, a backing layer similar to that used in Example 5 was provided on the side opposite to the photographic layer, and photosensitive material samples 1701 to 1708 were prepared corresponding to each of the underlayer coating solutions 1 to 8.

[0276] Each of the obtained samples 1701 to 1708 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 18. Note that the relative sensitivity is expressed with comparative sample 1701 as 100.

0277]

[Table 18]

[0278] As is clear from each of Examples 15 to 17, the polyethylene terephthalate film using the boron polymer of the present invention as a subbing layer as in the present invention has excellent antistatic performance, transparency, and photographic performance. Excellent in this respect.

Example 18 Polyethylene terephthalate was produced from a T-die at 280°C.
Melt and extrude it into a film shape and apply an electrostatic charge to it for about 30 minutes.
A coating solution having the following composition was applied to both sides of the unstretched film obtained by rapid cooling on a cooling drum at 75°C.
Preheated to 100°C, stretched longitudinally, then stretched horizontally at 100°C, and further stretched at 22°C.
After heat setting at 0° C., the film was cooled to obtain a biaxially stretched polyethylene terephthalate film treated with a sublayer and having a film thickness of 0.5 g/m 2 (in terms of polymer).

Coating liquid composition Water-dispersed polymer (vinylidene chloride/methyl acrylate/itaconic acid = 83/15/2)

63g/liter Surfactant (Triton
770)
1g/liter saponin

5g/liter
Boron polymers of the present invention (shown in Table 19)
7g/liter

[0281] Furthermore, a coating solution having the following composition was coated to a dry film thickness of 0.1 μm on the treated support whose underlayer had been subjected to corona discharge treatment at 8 W/m2·min.

Coating liquid composition Gelatin
10g/liter
Surfactant S-47
0.2g/liter
S-48
0.2g/liter Hardener
H-3
0.1g/liter Silica particles with an average particle size of 3μ 0.1g/liter

[
[0283] A photographic layer was provided on one side of the polyester film support after coating the undercoat layer obtained above using a coating solution having the composition of multilayer photographic material formulation 3 used in Example 3. In addition, a backing layer was provided on the side opposite to the photographic layer using the backing layer coating solution B-1 used in Example 3. Photosensitive material sample 180
1 to 1805 were created respectively.

[0284] Each of the obtained samples 1801 to 1805 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 19. Note that the relative sensitivity is expressed with comparative sample 1805 as 100.

0285]

[Table 19]

Example 19 A photographic layer was coated on both sides of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 18 using a coating solution having the composition of the multilayer photographic material formulation 4 used in Example 4. Photosensitive material samples 1901 to 1905 were prepared.

[0287] Each of the obtained samples 1901 to 1905 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 20. Note that the relative sensitivity is expressed with comparative sample 1905 as 100.

0288

[Table 20]

Example 20 A photographic layer was coated on one side of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 18 using a coating solution having the composition of the multilayer photographic material formulation 1 used in Example 1. Established. Further, a backing layer similar to that used in Example 5 was provided on the side opposite to the photographic layer to prepare photosensitive material samples 2001 to 2005.

[0290] Each of the obtained samples 2001 to 2005 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 21. Note that the relative sensitivity is expressed with comparative sample 2005 as 100.

0291

[Table 21]

[0292] As is clear from each of Examples 18 to 20, the polyethylene terephthalate film using the boron polymer of the present invention as a subbing layer as in the present invention has excellent antistatic performance, transparency, and photographic performance. Excellent in this respect.

Example 21 Subbing treatment-1 Polyethylene terephthalate with an intrinsic viscosity of 0.65 dl/g was melted and extruded into a film at 280°C from a T-die, electrostatically applied, and rapidly cooled on a cooling drum at about 30°C. The unstretched film (thickness 1000 μm) obtained by
After preheating and longitudinal stretching (3 times), coating solutions 1 to 8 having the composition shown in Table 22 below were applied to a corona discharge treated and surface treated support.
was applied to both sides, dried and preheated in a tenter, stretched horizontally (3 times) at 100°C, and then heat-set at 220°C.
After cooling, a subbed-treated biaxially stretched polyethylene terephthalate film having a film thickness of 0.3 g/m2 (in terms of polymer) was obtained.

[0294] Subbing treatment-2 Furthermore, 8W/
A coating solution having the following composition was applied onto a treated support that had been subjected to a corona discharge treatment of m2·min to a dry film thickness of 0.1 μm.

Coating liquid composition Gelatin
10g/liter Surfactant S-47
0.2g/liter
S-48
0.2g/liter Hardener H-3
0.1g/liter Silica particles with an average particle size of 3μ
0.1 g/liter Boron polymer of the present invention (Table 22) Table 22 description

0296
]

[Table 22]

[0297] A photographic layer was provided on one side of the polyester film support after the undercoat layer obtained above was coated with a coating solution having the composition of the multilayer photographic material formulation 3 used in Example 3. Further, a backing layer was provided on the side opposite to the photographic layer using backing layer coating liquid B-1 used in Example 3, and coating liquid No. 1
Photosensitive material samples 2101 to 2108 corresponding to each of ~8
It was created.

[0298] Each of the obtained samples 2101 to 2108 was exposed to light in the same manner as in Example 3, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 23. Note that the relative sensitivity is expressed with comparative sample 2101 as 100.

0299]

[Table 23]

Example 22 Photographic layers were provided on both sides of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 21 using a coating solution having the composition of multilayer photographic material formulation 4 used in Example 4. , coating liquid No. Photosensitive material samples 2201 corresponding to each of 1 to 8
~2208 were created respectively.

[0301] Each of the obtained samples 2201 to 2208 was exposed to light in the same manner as in Example 4, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 24. Note that the relative sensitivity is expressed with comparative sample 2201 as 100.

0302]

[Table 24]

Example 23 A photographic layer was provided on one side of a polyester film support after coating with a subbing layer prepared in the same manner as in Example 21 using a coating solution having the composition of the multilayer photographic material formulation 1 used in Example 1. Ta. Further, a backing layer similar to that used in Example 5 was provided on the side opposite to the photographic layer, and coating liquid No. Photosensitive material samples 2301 to 2308 were prepared corresponding to each of Examples 1 to 5, respectively.

[0304] Each of the obtained samples 2301 to 2308 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 25. Note that the relative sensitivity is expressed with comparative sample 2301 as 100.

0305]

[Table 25]

[0306] As is clear from each of Examples 18 to 20, the polyethylene terephthalate film using the boron polymer of the present invention as a subbing layer as in the present invention has excellent antistatic performance, transparency, and photographic performance. Excellent in this respect.

Example 24 One side (front surface) of a cellulose triacetate film support was subjected to subbing processing, and then the following No. 1 The layer coating solution was applied at a concentration of 20 ml/m2 as shown in Table 26, and dried at 80° C. for 5 minutes.

0308 Coating liquid for first layer (A) Ionene type polymer (see below)
35 g ethylene glycol
270ml
methanol
600ml acetone
4000 ml Boron polymer of the present invention (Table 26) Table 26 description

030
9]

[Chemical formula 48] First layer coating liquid (B) Alumina sol AS-100 (manufactured by Nissan Chemical Industries, Ltd.) 40 g Acetone

500ml methanol
400ml
dimethylformamide
100ml
Boron polymer of the present invention (Table 26)
Listed in Table 26 First layer coating liquid (C) Diacetylcellulose
1 g
SnO2 fine particles (average particle size 0.1 μm)
200mg acetone

500ml
methanol
200ml ethyl acetate

300ml Boron polymer of the present invention (Table 26) Table 2
6 Description 1st layer coating liquid (D) Vinylbenzyl quaternary ammonium salt copolymer (below) 7.5 g Diacetylcellulose
30 g acetone

550ml
methanol
45
0ml Boron polymer of the present invention (Table 26)
Listed in Table 26

0310]

[Chemical Formula 49] On the first layer obtained above, the following coating solution for the second layer was applied at a concentration of 20 ml/m2 as shown in Table 26, and the mixture was heated at 80°C.
and dried for 5 minutes.

0311 Second layer coating liquid (a) diacetyl cellulose
1 g acetone
500ml
Ethyl acetate
500ml

[0312] Further, on the second layer, apply the following third layer coating solution at 20% as shown in Table 26.
Apply to ml/m2, air temperature 75℃,
It was dried for 15 seconds with a vertical flow of drying air having an overall heat transfer coefficient of 40 kcal/m2·hr·°C.

Coating liquid for third layer: 1 part by weight of polyoxyethylene lauryl ether was mixed with 50 parts by weight of water heated to 90°C, and 10 parts by weight of carnauba wax (melting point 83°C) was separately melted at 90°C. After this was added, the mixture was stirred for 5 minutes using a high-speed stirring homogenizer, and 950 parts by weight of water, 750 parts by weight of methanol, and 50 parts by weight of 1-methoxy-2-propanol were added and mixed to form the third layer. I got the liquid.

A photographic layer was coated on the subbing layer of the thus prepared subbed cellulose triacetate support using a coating solution having the composition of the multilayer photographic material formulation 1 used in Example 1, and photosensitive material sample 2401 was applied. ~2426 were created respectively.

[0315] Each of the obtained samples 2401 to 2426 was exposed to light in the same manner as in Example 1, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 26. Incidentally, the relative sensitivity was expressed by setting the sample on the same day of coating as 100.

0316

[Table 26]

0317]

[C50]

Example 25 A photographic layer was coated on the subbing layer of a cellulose triacetate support prepared in the same manner as in Example 24 using a coating solution having the composition of the multilayer photographic material formulation 2 used in Example 2, and Photosensitive material samples 2501 to 2526 were prepared, respectively.

[0319] Each of the obtained samples 2501 to 2526 was exposed to light in the same manner as in Example 2, and then the relative sensitivity, haze, and surface resistivity of the obtained samples were evaluated in the same manner as in Example 5. The results are shown in Table 27. The relative sensitivity was expressed with the sensitivity of the same-day sample as 100.

0320]

[Table 27]

0321]

embedded image As is clear from each of Examples 24 and 25, the cellulose triacetate film using the boron polymer of the present invention in the subbing layer has excellent conductivity without affecting photographic performance (storability) or haze. Show your gender.

Example 26 Boron polymer No. 2 of the present invention 65 parts by weight and 95 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.65 were melt-kneaded in a co-rotating twin-screw kneading extruder (ZCM53/60 manufactured by Automatic Co., Ltd.) and then pelletized.

[0323] The pellets were vacuum dried at 180°C for 6 hours, then melted in an extruder and extruded from a slit die onto a rapidly cooling rotary drum to form an amorphous sheet with a thickness of 1.4 mm. ℃, stretched 2.6 times, then stretched 3.0 times in the transverse direction at 110℃, then heat-set at 210℃, then relaxed 0.5% in the transverse direction, and then cooled to obtain a film with a thickness of 180 μm. A support was obtained.

[0324] Next, this support was subjected to undercoating processing, and a photographic layer was coated with a coating liquid having the composition of multilayer photographic material formulation 3 used in Example 3 or photosensitive material formulation 4 used in Example 4. Photosensitive material samples 2601 and 2602 were prepared, respectively. In addition, in the above, boron polymer No. of the present invention. 6
Photosensitive material samples 2603 and 26 were prepared in the same manner except that 10 parts by weight of tin oxide and 90 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.65 were used instead of 5 parts by weight and 95 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.65.
04 were created respectively. Furthermore, a photosensitive material sample 2 was prepared in the same manner except that 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.65 and not containing the boron polymer of the present invention was used.
605 and 2606 were created respectively.

[0325] Each of the obtained samples 2601 to 2606 was processed using the processing method for each photosensitive material formulation (the sample using photosensitive material prescription 3 was processed in the same manner as in Example 3, and the sample using photosensitive material prescription 4 was processed in the same manner as in Example 3). 4), the resulting samples were evaluated for relative sensitivity, haze, and antistatic performance in the same manner as in Examples 1 and 5. The results are shown in Table 28. Note that the relative sensitivity is expressed with comparative sample 2605 as 100.

0326]

[Table 28]

Example 27 Cellulose triacetate (bound acetic acid amount 61.4%) 1
00 parts, methylene chloride 550 parts, methanol 33
1 part of triphenyl phosphate, 1 part of dye, and the boron polymer of the present invention (amounts shown in Table 29) were added to this solution and dissolved, followed by filtration and defoaming. , the dope was prepared. This dope was passed from the die to two drums with a length of 6 m.
It flowed down onto an endless stainless steel belt having a width of 0.3 m and maintained at 27°C. The speed of the stainless steel belt at this time was 5 m/min, and the dope flow rate was 100 cc/m. After that, dry it at 50℃, peel it off from the belt,
The base was dried at 20°C for 10 minutes.

Next, one side (surface) of the obtained cellulose triacetate film was subjected to subbing processing, and a color negative emulsion similar to that used in Example 1 was applied to prepare photosensitive material samples 2701 to 2708, respectively. After each of the obtained samples 2701 to 2708 was processed in the same manner as in Example 1, the photographic performance (storability), antistatic property on the back side (ash adhesion test), and haze after development were evaluated as in Examples 1 and 5.
Measured according to The results are shown in Table 29. However, the relative sensitivity is shown with the sensitivity of the sample on the day of application of each sample as 100.

0329]

[Table 29] Comparative compound 1 SnO2 fine particles described in JP-A-56-143431

0
330]

embedded image From each of Examples 26 and 27, it was found that when the boron polymer of the present invention was added to the support, good antistatic properties could be imparted without adversely affecting storage stability and haze.

0331]

[Effects of the Invention] As explained in detail above, the N of the present invention
By using a charge transfer type boron polymer having a -B complex structure, it is possible to provide a photographic material that satisfies photographic performance and transparency and has sufficient antistatic ability.

Claims (5)

[Claims] 1. A photographic material that is antistatic with a charge transfer type boron polymer having an N-B complex structure. 2. The photographic material according to claim 1, wherein the support contains a charge-transfer type boron polymer. 3. A photographic material according to claim 2, wherein the support is a plastic film. 4. The photographic material according to claim 1, wherein a charge-transfer type boron polymer is contained in the undercoat layer. 5. The photographic material according to claim 1, wherein the charge-transfer type boron polymer is contained in the hydrophilic colloid layer.